Di-thiocarbamyl-pyridines



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United States Patent Dffice 293W Patented May 24, 1960 EXAMPLE?! 2'-di-rh b I ridi ,0 ,5 :ocaromypy me Francis E. Cislak, Indianapolis, Ind nssignor to Rellly Tar 8: Chemical Corporation, Indianapolis, Ind., a corpontion of Indiana No Drawing. Filed June 10, 1959, Ser. No. 819,219 10 The procedure of Example 1 is repeated with the exception that 2,5-dicyanopyridine is used instead of the 5 Clllms. as dicyanopyri i e.

B m-rmocmmvnrvamnsas s a H N g i z-mrr N EXAMPLE 4 This invention relates to new compositions of matter, 15 v and to the process of making them. More particularly, Ladwhlocarbamylpyfldm it relates to di-thiocarbamylpyridines, which compounds have the general formula: ng

5 8 go rim-g l-NB: Magus. N

The procedure of Example 1 is repeated with the exception that 2,6-dicyanopyridine is used in place of the My new compounds may be conveniently made by the 3,5-dicyanopyridine. reaction of a dicyanopyridine with ammonium sulfide. 25 The equation below portrays the formation of 3,5-di- EXAMPLES thiocarbamylpyridine from 3,5-dicyanopyridine:

2,4-di-thiocarbamylpyridine I No on mix-E (E-rm, so a (mm-s 0 k N N/ illustrative of the manner in which my invention may be practiced I cite the following examples. N (gt-NH:

EXAMPLE 1 sfidiqhiocarbamylpyfldme The procedure of Example 1 is repeated with the exception that 2,4-dicyanopyridine is used in place of the s 3,5-dicyanopyridine. Bibih-Nn, My di-thiocarbamylpyridines are useful in controlling the action of non-oxidizing inorganic acids upon metals.

A Sisghrtfim of m di-thiocarbam l ines 1 boiling coal-tar bases is particularl useful in inhibitin 100 grams of 3,5-dicyanopyridine is dissolved in 1000 the action of rlute a ueous sulfuric acid u on grams of 30% ammoniacal methanol. The resulting e avior of my di-thiocarbamylpyridines indicates solution is saturated with dry H S at 25 C. and then that they exist in two tautomeric forms. Thus, 3,5-dipermitted to stand at room temperature for about two thiocarbamylpyridine, in its reactions, functions as either days. The di-thionicotinamide formed during this time of the tautomeric forms shown below: is separated from the mother liquor by filtration. For most purposes the product so obtained is pure enough.

a s s B If a purer product is desired, it may be obtained by re- KIN- J J-NHI HN-J: d-NB crystallizing the semi-pure compound from suitable sol- 2 86 N N I II vents, such as water, water-acetone, pyridine, or dimethylforamide.

The 3,5-dithionicotinamide is a high melting crystallme sohd ham ayeuow color The presence oftwo thiol groups in the molecule of EXAMPLE 2 my di-thiocarbamylpyridines makes them useful for the preparation of co-ordigtjon polymers" by treatment 3,4-di-thiocarbamylpyridin: with suitable metal salts to form metal derivatives. 9 Such polymerizations may be carried out by chelation i with zinc (11), copper (II), and nickel (II) ions. The M 5 structure of these polymers is portrayed below:

m1 NB NB 1am aka-d b-s-u-s-d c-s-M-s- N N N n The procedure of Example 1 is repeated except that to 3,4-dicyanopyridine is used in place of the 3,5-dicyano- These polymers are characterized by stability at lush pyridine. temperatures.

-3; 'Ih'compound 2,6-di-thiocirbamylpyridine.

The gompound 2,5,-di-thiocarbamylpyridine. 5. The compound 3,4-di-thi0carbamylpyridine.

1 01mm is'ifif im iehiidnz l. Di-thiocarbamylpyridines having the .stmctural 0.

formula 5 References Cited in the file of this patent W UNITED STATES PATENTS 2,500,142 Wicsehahn Mar. 7, 1950 2,560,046 Alliger July 10, 1951 2. The compound 3,5di-thiocarb'amylpyriding, 2,653,942 lLec Sept. 29, 1953 

1. DI-THIOCARBAMYLPYRIDINES HAVING THE STRUCTURAL FORMULA: 